Process of producing olefine hydrocarbons and derivatives thereof



Oct. 2, 1934.v H. B. HAss ET AL PROCESS 0F PRODUCING' OLEFINE HYDROCARBONS AND DERIVATIVES THEHEOF Filed Jan. 8, '1932 Patented Oct. 2, l1934A PROCESS F PRODUCING OLEFINE HYDRO- CARBONS AND DERIVATIVES THEREOF Henry B. Hass and Paul E. Weston, West Lafayette, Ind., assignors to Purdue Research. Foundation, West Lafayette, Ind., a'corporation of Indiana y Application January 8, 1932, Serial' No. 585,548

Claims.

It is the object of our present invention to produce straight-chain oleiines of from 4 to 5 carbon atoms economically and substantially free from the impurities which are formed in hitherto knowncommercial processes of olene production; so that the comparativelypure olenes thus obtained may be used directly. for the manufacture of `high-grade alcohols, esters, glycols, and otherl products. By straightchain' we mean that the chain of carbon atoms is unbranched; as distinguished from the iso -or other branched-chain compounds, in which there is a branching in the chain of carbon atoms.

Our process may produce various isomers; but that is often immaterial, as the derivatives which may be obtained from the various isomers are oftentimes the same-such for instance as secondary butyl alcohol, which is ,obtainable either from 1buteneor from 2-butene or from a mixture of 1butene and 2butene. The production or non-production of isomers is at least largely controllable, as catalysts are or are not used.

In carrying out our invention, we subject straight-chain alkyl halidesof the middle halo; gensthat is, alkyl chlorides or alkyl bromidesof from 4 to 5l carbon atoms to pyrolysis at high temperatures, above 450 C. and desirably b@- tween 500 and 650 C. if no catalyst is used, but somewhat lower than that if a catalyst is used. This causes splitting of the molecule to produce a straight-chain olefine and a hydrogen halide. We then quickly cool the resultant mixture, to minimize the reversal of the reaction and the formation of decomposition products such as occurs on slow cooling, The hydrogen halide obtained is separated, and is a valuable by-product which in itself is often of suicient value to cover the cost of the initial reagents used. Then A the olenes obtained are suitably separated from the unreacted alkyl haliges, and the latter may be re-cycled.

In the drawing we show an apparatus suitable for carying out our process, although other apparatus may be used.- In such drawing, the single figure is a diagrammatic view showing 'such apparatus.

We `will describe this` apparatus primarily in connection with the obtaining of butenes.

AThe desired parain hydrocarbonbutane or pentane-may be halogenated in any desired manner, with either middle halogen. We desirably use Jchlorine as'the halogen, although we may use bromine. I1' butane is the starting hy-l drocarbon, it may be chlorinated in any known manner, to form chlorobutanes. We use mono- (ol. 26o-170) (l) CHT CHT CH2; CHQ-I-Clz-)CHgCl' CHT CHz- CHM-HC1,

butane l-chlorobutane (2) CH3- CHT CHT CHa-l-Ch-)CHI- CHOI' CH2 CHM-HC1 butane 2-chlorobutane Usually there is a mixture formed consisting in part of l-chlorobutane shown as a result of Equation (l) and 2-chlorobutane shown as a 70 resultsof Equation (2). 'Ihese chlorobutanes are liquid at room temperature.

Either of these monochlorobutanes, or a, mixture of them, maybe placed in a container 10, and fed thence, under the control VVof a valve 11, to a preheating tube 12 in which vaporization occurs. The tube 12 may be maintained at a temperature somewhat above the .boiling points of the monochlorobutanes", (which are respectively about 78 C. and 68 C.,) and con- 30 veniently at'about 300 C., as by being immersed in a' bath 13 of molten salts held at the desired temperature. n

From the tube l2, the vaporized monochloro` butanes pass to and through a reaction tube 14. This tube is maintained at such temperature that pyrolysis quickly occurs therein; and is of such length that the reaction time is sufficiently long to produce at least"80% yield of butenes but desirably su'iciently short to prevent material decomposition of the butenes produced. The

\ desirable reaction time decreases as the temperature is increased. We have found that exfcellent results with a mixture of monochlorobutanes may be obtained by maintaining the temperature of the tube 14 at 600 C.i10. The flow of` vapors through the reaction tube 14 is desirably such that the vapors pass through in less than 3.0 seconds and desirably in about 1.5 seconds, which gives about 80% yield of very 100 pure butenes. Those conditions vary somewhat for dilerent alkyl halides, but the value given is a desirable one `for pyrolyzing monochlorobutanes. The desired temperature of the reac- -tion tube ymay be obtained by having it immersed in a bath 15 of molten lead, or of suitable molten salts.

In theA reaction tube 14 the monochlorobutanes are pyrolyzed to form hydrogen chloride and a, mixture of butenes. If no catalyst is present,

the reactions are shown by the following equations: i

(a) CHZCLCHTGHrCHcHrCH-CHTGEH-HC1 l-chlorobutane l-butene (4) oHycHcLcHz-cHa-)Cmcn- ABrera-knol z-chlorobutane l-butene (5) CH3-onorCH2-oHHoHycmcH-cnwnol 2-chlorobutane 2-butene Thus the l-chlorobutane on pyrolysis produces l-butene and hydrogen chloride; while the 2- chlorobutane produces some l-butene and some 2-butene, in addition to hydrogen chloride. The 2butene may be either one of two alloisomerscis-2-butene and trans-2-butene; so that in the process there are three butenes formed simultaneously, in proportions which depend on conditions. We can if necessary separate those three butenes, as by rectification; but ordinarily it is not necessary to separate them.

By using calcium chloride as a catalyst in the pyrolysis, a tendency arises to promote the formation of 2-'butene, possibly by a shifting of the double bond as indicated by the following equation:

(o) CI-IpcI-IcH2-cH-cH3CH;CHCHa Thus, when the pyrolysis was made ofl 1- chlorobutane alone: if without a catalyst, the

butene was obtained; lif with CaClz as a catalystat a reaction temperature of 450 C., a mixture of about 15% l-butene and 85% 2-butene was obtained; and if with CaClz as a catalyst at a reaction temperature of 400 C., a butene which was at least 95% 2-butene was obtained.

'Ihe reactions shown in Equations 3,4, and A5 are reversible, depending on temperature, and tend to go the other way from that indicated if the temperature is lowered slowly. Also, if the gases are maintained at the high reaction temp erature for any material length of 4time following the reaction, there are various side reactions that tend to produce unwanted products.

Therefore, on passing from the discharge end of the reaction tube 14 the mixture of hot gases is immediately cooled. Tp this end, such mixture is passed directly from such discharge end to a cooling coil 20, in a cooling 4jacket 21 through which cold brine or water ows; and it is there quickly reducedto room temperature or below, desirably to about 20 C. The cooled gases from the cooling coil 2 0 pass to a counter-current water-scrubber 22. The water takes up the hydrogen chloride which has been formed, and passes out at the bottom through a valved discharge pipe 23 into a suitable receiver 24. 'I'he hydrochloric acid thus obtained is a valuable byproduct, and in, it practically half of the chlorine used in the original chlorination of the hydrocarbon is recovered. The butenes, and any unreacted monochlorobutanes, pass by a pipe 25 from the top of the water-scrubber 22, desirably through an alkali scrubber 26, to the middle of a.' continuous rectifying column 27, the temperatures within which are controlled so as to separate the butenes from such unreactedvmoncchlorobutanes. This is readily done, as the butenes boil between -6.7 and +3.0 C., while as already stated the monochlorobutanes have boiling points of about 78 and 68 C. respectively.

The condensed monochlorobutanes pass from the bottom of the rectifying column 27 to a return pipe 28, in which is apump 29. The pipe 28 leads back to the entrance to the pre-heating tube 12, to re-cycle the unreacted monochlorobutanes. The puried butenes pass from the top of the rectifying column 27 by a pipe 30 to a pump 31, and thence through a condensing coil 32 into a collecting receptacle 33. The pump 31, assisted somewhat by the pump 29, maintains the iiow of uids through the system. The pumps also serve to keep the pressure in the reaction tube 14 at about atmospheric pressure, which we find desirable for the proper reaction for greater pressure retards the reaction, and less pressure tends to admit air with the accompanying danger of explosion.

As we have already stated, instead of using chlorobutanes as our 'starting alkyl halide, we may use bromine as the halogen and/or the pentyl radicals, to provide various m'onobromobutanes, monobromopentanes, and monochloropentanes, as the starting alkyl halide. the pyrolysis in the reaction tube 14 may give hydrobrom acid; as a by-product instead of hy- In such cases.

drochloric acid, and the oleiines produced will be butenes or pentenes as the case may be.

For instance bromo-pentane (either l-bromopentane, Z-brOmO-pentane, B-bromo-pentane, or a mixture of two or all of these,) may be vaporized, and the vapor passed at a pressure at about atmospheric pressure through the reaction tube 14, while the latter is held at a temperature of 500 C.i10. The vapor is passed at such a rate that it remains for a suitable time in the reaction tube. The pyrolysis of l-bromopentane occurs relatively slowly, and if it is used the reaction time at 500 C. is desirably at least 10 to 20 seconds. `The pyrolysis of z-bromopentane and. 3-bromopentane occurs relatively rapidly, and ify they are used the reaction time at 500 C. is desirably about 1.5 to 2 seconds.

The vapors issuing from the reaction tube 14 are cooled rapidly, tb about 40 C., in the cooling coil 20; and the cooled fluid is then passed to the Water-scrubber 22, -desirably maintained at aboutv the same temperature, in which the water takes up the hydrogenbromide. The pentenes (amylenes) are gaseous at this temperature (40 C.), and pass .out through the pipe 25 and the alkali scrubber 26 to the middle of the rectifying column 27. The unreacted bromopentanes are liquid at .the temperature of the water-scrubber, so that a portion of them passes from' the bottom thereof with the water solution of hydrogen bromide. A container 35 may be provided in the pipe 23 to receive this mixture ofliquids, and to hold them with'suiicient quiet to let them separate by gravity into two layers, for they are not miscible. The upper layer usually contains the unreacted bromopentanes, and the lower layer the water solution of hydrogen bromide; although it is possible to reverse this order if there is excess water. The two layers are drawn off from the upper. and lower levels respectively, of the container 35, the water solution of hydrogen bro- ,mide (hydrobromic acid) passing to the receiving container 24, while the bromopentanes pass to an linlet near the bottom of the rectifying column 27 by way of a valved pipe 36 and desirably an alkali scrubber 37. (The valve in the pipe 36 is opened or closed according to whether the unreacted alkyl halides are liquids or vapors at the temperature of the water-scrubber 22.) The rectifying column 27 separates more completely the unreacted bromopentanes from the pentenes: and the former pass back by the pipe 28 and pump 29 for re-cycling, while the latter pass through the pumpl and cooling coil 32 to the final olene receiver 33.

No catalyst is necessary with our process, but a catalyst may be used where and if desired. For instance, in producingany of these olenes mentioned, granulated anhydrous calcium chloride may be used in the reaction tube 14. If la catalyst is used, its amount, by weight, is desirably between 50% and 100% of the weight of vapors passed through the reaction tube per hour. The catalyst makes it possible to use lower reaction temperatures. The desirable reaction temperavture will vary according to the materials being worked upon, and according to the presence or absencel of a. catalyst and its nature. Such desirable temperature may in general be` stated If thel temperature is markedly below such point,

the reaction time is materially increased. We

have foundit desirable to have the reaction temperature above 450 C. if no catalystis used, and

above 200 C. if CaClz is used as a catalyst.

Further, the temperature should not be so 4high that the pyrolysis goes markedly beyond,

the production of the desired olenes, to produce further split-products; as will be obtained if too high a temperature is used. We find that the maximum desirable temperature l is about 700 C. if no catalyst is used, and about 650 C. if CaClz is used as a catalyst..

When the pyrolysis above described is carried out a slight carbonaceous deposit sometimes forms very slowly in the reaction'tube 14. This is due to a fractional decomposition. It is ordinarily not bothersome in the absence of a catalyst; but in the presence of a catalyst, such de.- posit gradually reduces the catalytic action. If such a carbonaceo'us deposit is formed, it can readily be removed by a brief lblowing of air through the reactiontube at the same temperature used for the pyrolysis. To avoid explosion, the reaction tube is first blown free of inflammable gas by some inert gas, such as nitrogen or steam or carbon dioxide.

The olenes, such as the butenes, which are obtained in the ultimate receiver 33 may be used in known Ways to produce alcohols, esters, glycols, etc. It is often not necessary to separate the isomeric olenes for doing this. For instance, both l-butene andZ-butene, when hydrated in the presence of sulfuric acid as a catalyst, yield secondary butyl alcohol; so that a substantially pure secondary butyl alcohol may be 'obtained from either l-butene or 2'butene, or from a mixture of those butenes.' v f f Although our present invention so far as it is directed to straight-chain the mere production of olenes by-pyrolysis of alkyl halides is limited to olenes having from 4 to l5 carbon atoms, it is not thus limited in 'the separation of the ole- ;nes from the co-produced hydrogen halides;

for from the viewpoint of separating olenes from hydrogen haldes, whether co-produced or not, our inventici extends to olenes having from 2 to 7 carbon atoms, such as ethylene', propene, butenes, pentenes, hexenes, and heptenes, from hydrogen chloride or from hydrogen bromide, all of which-are producible by pyrolysis in -our apl paratus of lalkyl halides of from 1 to 7 carbon atoms.

We claim as our invention:

, 1. The .process of producing an olene, which consists in subjecting a straight-chain alkyl halide of from 4 to 5 carbon atoms and of one of the middle halogens to non-catalytic pyrolysis at a temperature above 450 C.

2. The process of producing an oleflne in ac cordance with claim l, where the alkyl halide is an alkyl chloride.

3. The process of producing an olefine in accordance with claim 1, where the alkyl halide is `a monochlorobutane.

4. The process of producing an olene in accordance with claim 1, where the alkyl halide is a monochloropentane.

l5. The process of producing an olene as set forth in claim 1, and immediately cooling the products of the pyrolysis.

6, The process of producing an olene, which consists in subjectingv a straight-chain ,alkyl halide of from 4 to 5 carbon atoms and of one of the middle halogens to non-catalytic pyrolysis at halide of from 4 to 5 carbon atoms and of one of the middle halogens to pyrolysis at a temperature sufficiently high so that the pyrolysis is complete in less than one minute. y

9. The process for manufacturingan alcohol,

'which consists in chlorinating a straight-chain paraflin hydrocarbon having from 4 to 5 carbon atoms to obtain a mixture consisting essentially of straight-chain monochloroparaflns, converting the mixture of straight-chain monochloroparaflins so produced to olenes by noncatalytic pyrolysis, and converting the olenes ,i

thus obtained to an alcohol by catalytic hydration.

10. The process for manufacturing an alcohol, which consists in halogenatingvwith a middle hal ogen a straight-chain parafin hydrocarbon having from 4 to 5 carbon atoms to obtain a mixture consistingv essentially of straight-chain monolhalogenated parans, converting the mixture of IENRY B. HASS'. PAUL E. WESTON.`

j 'CERTIFICATE 0F CORRECTION.

Patent No. 'i,975,456. A OctoberZ, 1934.

HENRY HAss, E r AL.

It is herebyl certified that error appears in the printed specification of lthe above numbered patent requiring correction as follows: Page 2, lineA 91, after the word "reactionfinsert a semicolon; and line v102, for "hydroorom" read hydrobromic; and page 3,'line'64, strike out thewords "straight-chain" and insert the same after "to" in line 65; and that the saidLetters Patent should be read with therev corrections therein that 4the same may conform to the record of thecase in the Patent Office.

Signed and sealed this 19th day of February, A. D.A 1935.

Leslie Frazer (Seal) Acting Commissioner olf Patents. 

